Halogen-containing organic stabilizers for 3-isothiazolones

ABSTRACT

A method of stabilizing 3-isothiazolones against chemical degradation in antagonistic environments by the use of certain activated halogen compounds is disclosed. Compositions including 3-isothiazolones and alkyl halohydantoins, halo-substituted triazinetriones, N-halosuccinimides, p-toluenesulfonyl halides, haloacetic acids and alkyl sulfamoyl halides are found to be particularly stable in metal working fluids and latex paints.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention concerns the stabilization of 3-isothiazolone compounds by the incorporation with those compounds of certain halogen-containing organic compounds.

2. Description of the Prior Art

Isothiazolones have generated high commercial interest as microbicides to prevent spoilage of certain aqueous and non-aqueous products caused by microorganisms. Isothiazolones are highly effective microbicides (as used herein, "microbicides" includes bactericides, fungicides and algicides and microbicidal activity is intended to include both the elimination of and the inhibition or prevention of growth of microbial organisms such as bacteria, fungi and algae); by suitable choice of functional groups, they are useful in a broad range of applications. However, it has been long recognized that either in storage prior to addition to the substrate to be treated or after addition, their efficacy may be decreased because they are not stable under practical conditions of long-term storage. Means have thus been sought for some time to improve the stability of isothiazolones.

U.S. Pat. Nos. 3,870,795 and 4,067,878 teach the stabilization of isothiazolones against chemical decomposition by addition of a metal nitrite or metal nitrate, but teach that other common metal salts, including carbonates, sulfates, chlorates, perchlorates, and chlorides are ineffective in stabilizing solutions of isothiazolones, such solutions usually being in water or in an hydroxylic solvent.

U.S. Pat. Nos. 4,150,026 and 4,241,214 teach that metal salt complexes of isothiazolones are useful because they have enhanced thermal stability, while retaining biological activity.

It is known to use certain organic stabilizers for isothiazolones, generally for use situations where metal salts may create problems, such as corrosion, coagulation of latices, insolubility in non-aqueous media, interaction with the substrate to be stabilized, and the like. Formaldehyde or formaldehyde-releasing chemicals are known as stabilizers, (see U.S. Pat. Nos. 4,165,318 and 4,129,448), as are certain organic chemicals such as orthoesters (U.S. Pat. No. 4,906,274) and epoxides (U.S. application Ser. No. 194,234).

Both formaldehyde or formaldehyde-releasers and salt stabilization have some drawbacks. In certain applications, however, it is desirable to avoid addition of certain organic stabilizers by virtue of their volatility, decomposition under high heat, higher cost, difficulty in handling, potential toxicity, and the like.

In actual use, copper salts, such as copper sulfate, have proved efficacious in the stabilization of isothiazolones. However, copper salts may be undesirable in effluent streams in such operations as in the manufacture of stabilized isothiazolones or in their blending into a product or the use of that product. Copper salts, especially the chlorides, may contribute to possible corrosion, or in the presence of polymers in aqueous dispersion may lead to coagulation of the dispersion.

Research Disclosure, 160, p. 28, #16047 (August 1977), describes antimicrobial synergy between certain activated halogen compounds and certain 3-isothiazolones, but does not disclose the use of the halogen compounds as stabilizers for 3-isothiazolones against chemical decomposition.

SUMMARY OF THE INVENTION

It is an object of the invention to provide a stabilization system for isothiazolones which overcomes some or all of the disadvantages of prior art systems. It is also an object to provide an isothiazolone stabilized by only low levels of stabilizer so as to avoid interference with other components in systems in which isothiazolones are used as microbicides.

These objects, and others which will become apparent from the following disclosure, are achieved by the present invention. It has been surprisingly found that isothiazolones may be stabilized against decomposition by the addition of certain halogen-containing organic compounds known as "activated" halogen compounds, to the composition containing the isothiazolone. Accordingly the invention provides in one aspect a composition comprising:

a) at least one 3-isothiazolone of the formula (I) ##STR1## wherein

Y is an unsubstituted or substituted (C₁ -C₁₈)alkyl, an unsubstituted or substituted (C₃ -C₁₂)cycloalkyl, an unsubstituted or halogen-substituted (C₂ -C₈)alkenyl or alkynyl, an unsubstituted or substituted (C₇ -C₁₀)aralkyl, or an unsubstituted or substituted aryl; and

R and R¹ is each independently H, halogen or (C₁ -C₄)alkyl; and

b) a halogen-containing organic compound selected from the group consisting of alkyl halohydantoins, halo-substituted triazinetriones, N-halosuccinimides, p-toluenesulfonyl halides, alkyl sulfoamoyl halides, and the like.

In another aspect, the invention comprises a method for stabilizing 3-isothiazolones against chemical degradation in antagonistic environments, such as metal working fluids, latex paint, bulk latex, cosmetic and surfactants.

In another aspect, the invention comprises a method for inhibiting or preventing the growth of a member selected from the group consisting of bacteria, fungi, yeast, algae in a locus subject or susceptible to contamination by said member, which comprises incorporating onto or into the locus, in an amount which is effective to adversely affect the growth of said member, the aforementioned composition.

DETAILED DESCRIPTION OF THE INVENTION AND THE PREFERRED EMBODIMENTS

The isothiazolones which are stabilized include those disclosed in U.S. Pat. Nos. 3,523,121 and 3,761,488 and are represented by the formula ##STR2## as defined above. In particular Y may be a (C₁ -C₁₈)alkyl or (C₃ -C₁₂)cycloalkyl each optionally substituted with one or more of hydroxy, halo, cyano, alkylamino, dialkylamino, arylamino, carboxy, carbalkoxy, alkoxy, aryloxy, alkylthio, arylthio, haloalkoxy, cycloalkylamino, carbamoxy, or isothiazolonyl; and unsubstituted or halo-substituted (C₂ -C₈)alkenyl or alkynyl; a (C₇ -C₁₀)aralkyl optionally substituted with one or more of halogen, (C₁ -C₄)alkyl or (C₁ -C₄)alkoxy; and an aryl optionally substituted with one or more of halogen, nitro, (C₁ -C₄)alkyl, (C₁ -C₄)alkyl-acylamino, carb(C₁ -C₄)alkoxy or sulfamyl.

Preferred substituents for Y are substituted or unsubstituted (C₁ -C₁₈)alkyl or (C₃ -C₁₂)cycloalkyl; R is preferred to be H, methyl or Cl; and R¹ is preferred to be H or Cl. Representative of such preferred Y substituents are methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, cyclohexyl, benzyl, 3,4-dichlorobenzyl, 4-methoxybenzyl, 4-chlorobenzyl, 3,4-dichlorophenyl, 4-methoxyphenyl, hydroxymethyl, chloromethyl, chloropropyl, hydrogen, and the like.

Particularly preferred isothiazolones are 5-chloro-2-methyl-3-isothiazolone, 2-methyl-3-isothiazolone, 2-n-octyl-3-isothiazolone, 4,5-dichloro-2-cyclohexyl-3-isothiazolone and 4,5-dichloro-2-octyl-3-isothiazolone.

Most preferred is 5-chloro-2-methyl-3-isothiazolone, either as a sole compound or in admixture with 2-methyl-3-isothiazolone. When in admixture, the preferred ratio of monochlorinated/unchlorinated isothiazolone is from about 70:30 to about 85:15, and an especially preferred ratio is from about 70:30 to about 80:20. A second especially preferred isothiazolone is 2-methyl-3-isothiazolone in combination with low levels of 5-chloro-2-methyl-3-isothiazolone, a preferred ratio being from about 98:2 to about 96:4, and an especially preferred ratio being about 97:3.

Preferred activated halogen-containing organic compounds are alkyl halohydanoins, halo-substituted triazinetriones, N-halosuccinimides, p-toluenesulfonyl halides, and alkyl sulfamoyl halides. Particularly preferred specific compounds include dichlorodimethylhydantoin, bromochlorodimethylhydantoin and N-bromosuccinimide.

Some halogen-containing organic compounds are known to have microbicidal activity, although their efficacy as stabilizers of isothiazolones has not previously been appreciated. Such compounds will be particularly desirable to use as stabilizers; examples are

1,3-dichloro-5,5-dimethylhydantoin and

3-bromo-1-chloro-5,5-dimethylhydantoin.

Among the activated halogen compounds which are useful for the stabilization of 3-isothiazolones in antagonistic environments are: N-halosuccinimides (N-bromosuccinimide, N-iodosuccinimide), haloalkylhydantoins (1,3-dibromo-5,5-dimethylhydantoin, 1,3-dichloro-5,5-dimethylhydantoin, 3-bromo-1-chloro-5,5-dimethylhydantoin), β-bromostyrene, α-chlorocinnamaldehyde, dimethyl sulfamoyl chloride, 2,2-dibromo-3-nitrilopropionamide, bromo-β-nitrostyrene, bis-(trichloromethyl)sulfone, p-tolyldiiodomethyl sulfone, 2-bromo-2-nitropropanediol, 5-bromo-2-nitro-1,3-dioxane, 1,2-dibromo-2,4-dicyanobutone, haloacetic acids (chloroacetic acid, bromoacetic acid, iodoacetic acid, trichloroacetic acid), p-toluenesulfonyl chloride, p-toluenesulfonyl chloramine sodium salt (Chloramine T), bromomaleic anhydride, trichloroisocyanuric acid (1,3,5-trichlorotriazinetrione), polyvinylpyrrolidone (povidone) I₂ complex, morpholine I₂ complex, 5-chlorobenzotriazole and ethyl dichlorophosphate.

The composition may contain from about 0.01 to about 99.9999 parts of the one or more isothiazolones, and from about 0.0001 to about 99.9 parts of the halogen-containing organic compound.

Generally, the composition of the invention will be in the form of a solution. Typical formulation ranges are illustrated in the following Table (all percentages are parts by weight) for both a concentrated solution of the isothiazolone and a dilute solution. For certain uses, such as shipping of large quantities, more concentrated solutions may also be utilized.

    ______________________________________                                         FORMULATIONS TABLE                                                                          Halogen-containing                                                Isothiazolone                                                                               Organic Compound                                                                              Solvent                                            ______________________________________                                         0.01-99.9999%                                                                               0.0001-99.9%    0-99.9899%                                        Preferred                                                                       0.1-50%      0.01-20%      30-99.89%                                          ______________________________________                                    

Solvents may be used to dissolve the isothiazolones and may be any organic solvent which dissolves the isothiazolones, is compatible with the proposed end use, does not destabilize the isothiazolone, and does not react with the halogen-containing organic compound to eliminate its stabilizing action.

Hydroxylic solvents, for example, polyols, such as glycols, alcohols and the like, may be used. Under conditions of high dilution and high ratios of stabilizer to isothiazolone, glycols may be successfully used. In certain formulations, hydrocarbons, either aliphatic or aromatic, are useful solvents.

Preferred solvents are capped polyols, wherein the free hydroxyl group is replaced with an ether or ester function. Especially preferred are 2,5,8,11-tetraoxadodecane, commonly known as triethylene glycol dimethyl ether, and 3,6-dioxadecanol-1 acetate, commonly known as diethylene glycol butyl ether acetate.

Water is a solvent for certain of the preferred isothiazolones and the halogen-containing organic compound may be employed in aqueous formulations.

The amounts of halogen-containing organic compound employed will vary depending on use conditions and concentrations of the isothiazolone in the mixture: effective amounts of halogen-containing organic compounds based on isothiazolone may be ratios in the range of from about 1:100 to about 1000:1 stabilizer to isothiazolone. In concentrated solutions, ratios are generally from about 1:50 to about 50:1. Obviously higher amounts may be used, but at additional cost. At high levels of dilution of the isothiazolone (such as from 1 to 10,000 ppm isothiazolone in the solvent), the ratio of stabilizer to isothiazolone can range from about 1:10 to about 20:1. The preferred range is from 1:1 to 20:1.

The stabilization advantages of the halogen-containing organic compounds of the present invention are noted even when the isothiazolone contains other salt stabilizers, such as those recorded in U.S. Pat. Nos. 3,870,795, 4,067,878, 4,150,026 and 4,241,214.

Uses of these new organically stabilized microbicides are typically at any locus subject to contamination by bacteria, fungi, yeast or algae. Typically loci are in aqueous systems such as water cooling, laundry rinse water, oil systems such as cutting oils, oil fields and the like where microorganisms need to be killed or where their growth needs to be controlled. However, these stabilized microbicides may also be used in all applications for which known microbicidal compositions are useful; preferred utilities of the compositions are to protect wood, paint, adhesive, glue, paper, textile, leather, plastics, cardboard, lubricants, cosmetics, food, caulking, feed and industrial cooling water from microorganisms.

The following lists typical industries and applications of compositions:

    ______________________________________                                         Industry       Application                                                     ______________________________________                                         Adhesives, sealants                                                                           adhesives                                                                      caulks                                                                         sealants                                                        Agriculture/food chain                                                                        adjuvant preservation                                                          agricultural active ingredient                                                 agricultural chemical preservative                                             agricultural formulations preservation                                         animal feed preservation                                                       dairy chemicals                                                                fertilizer preservation                                                        food preservation                                                              food processing chemicals                                                      grain preservation                                                             post-harvest produce protection                                                sugar processing                                                               tobacco                                                         Construction products                                                                         asphalt/concrete                                                               cement modifiers                                                               construction products                                                          roof mastics                                                                   synthetic stucco                                                               wall mastics                                                                   joint cement                                                    Cosmetics and toiletries                                                                      cosmetics                                                                      raw materials for cosmetics, toiletries                                        toiletries                                                      Disinfectants, antiseptics                                                                    antiseptic                                                                     disinfectant                                                    Emulsions, dispersions                                                                        aqueous dispersions                                                            dispersed pigments                                                             latex                                                                          photographic emulsions                                                         pigment slurries                                                               polymer latices                                                 Formulated household                                                                          fabric softeners                                                products       polishes                                                                       waxes                                                                          hand dish detergents                                                           raw materials                                                                  liquid detergents                                                              hand soaps                                                      Industrial processing, misc                                                                   electrodeposition paint, baths, rinses                                         electrodeposition pre-treatment, post                                          rinses                                                                         industrial fluids preservation                                                 pasteurization baths                                                           process aid preservation                                        Industrial water treatment                                                                    air washers                                                                    cooling towers                                                                 cooling water                                                                  water cooling                                                                  preservation/treatment of wooden                                               cooling tower slats and structural                                             members                                                                        can warmers                                                                    brewery pasteurization                                                         closed loop water cooling systems                               Laundry        household laundry products                                                     laundered goods                                                                laundry rinse water                                                            sanitizers-laundry                                              Leather, leather products                                                                     leather and hide                                                               leather and hide products                                       Lubricants, hydraulic aids                                                                    automotive lubricants and fluids                                               conveyor lubricants                                                            greases                                                                        hydraulic fluids                                                               lubricants                                                      Medical devices                                                                               diagnostic enzymes                                                             diagnostic kits                                                                medical devices                                                 Metalworking & related                                                                        cutting fluids                                                  app's          metal cleaning                                                                 metalworking fluids                                             Odor control (active                                                                          air conditioning                                                ingredient)    animal bedding                                                                 cat litter                                                                     chemical toilet prep'ns                                                        deodorizers                                                                    humidifiers                                                                    industrial deodorants                                                          sanitary formulations                                                          toilet bowls                                                    Paints and coatings                                                                           emulsions                                                                      paints                                                          Paper and wood pulp,                                                                          absorbant materials of paper                                    their products and wood pulp                                                                  packaging materials of paper                                                   and wood pulp                                                                  paper                                                                          paper products                                                                 paper treatment                                                                soap wrap                                                                      wood pulp                                                                      wood pulp products                                              Paper mill     paper mill slimicides                                                          pulp and paper slurries                                         Petroleum refining, fuels                                                                     aviation fuels (jet fuel, aviation gas)                                        crude oils                                                                     burner, diesel and turbine fuel oils                                           coal slurries                                                                  diesel fuel additives                                                          diesel fuels                                                                   fuels                                                                          gasoline                                                                       heating oils                                                                   hydrocarbons                                                                   kerosene                                                                       liquified petroleum gas                                                        petrochemical feedstocks                                                       petroleum products, storage,                                                   transportation and production                                                  recycled petroleum products                                                    residual fuel oils                                                             turbine oils                                                    Photographic chemicals                                                                        photographic processing-wash water,                             and process    rinses                                                                         photoprocessing                                                                photoplate processing chemicals                                                (developers, stabilizers etc)                                   Printing       fountain solutions (printing)                                                  ink components (pigments, resins,                                              solvents, etc)                                                                 inks                                                            Sanitizers (active)                                                                           sanitizers                                                                     sanitizers-dairy                                                               sanitizers-dental                                                              sanitizers-fermentation                                                        sanitizers-food preparation                                                    sanitizers-food processing                                                     sanitizers-medical                                                             sanitizers-rendering                                                           sanitizers-veterinary                                           Soaps, detergents, cleaners                                                                   cleaners                                                                       detergents                                                                     household cleaners                                                             industrial cleaners                                                            liquid soaps                                                                   oil and grease remover                                                         powdered soaps                                                                 raw materials for cleaning products                                            soaps                                                                          surfactants                                                     Textiles, textile products                                                                    bonded fabrics                                                                 burlap                                                                         canvas                                                                         canvas goods                                                                   carpet backing                                                                 carpets                                                                        clothing                                                                       coated fabrics                                                                 curtains                                                                       draperies                                                                      engineering textiles                                                           fibers                                                                         geotextiles                                                                    goods made of textiles                                                         knitted fabrics                                                                nets                                                                           nonwoven fabrics                                                               rope                                                                           rugs                                                                           textile accessories                                                            textile products                                                               textiles                                                                       upholstery                                                                     woven fabrics                                                                  yarn                                                            Textile processing                                                                            dye fixatives                                                                  dyes                                                                           fiber lubricants                                                               hand modifiers                                                                 sizes                                                                          textile processing fluids                                       Therapeutic (active or                                                                        animal health/veterinary                                        preservative)  aquaculture                                                                    dental                                                                         human health                                                                   pharmaceutical/therapeutic                                      Water purification                                                                            charcoal beds                                                                  deionization resins                                                            filters                                                                        membranes                                                                      reverse osmosis membranes                                                      ultrafilters                                                                   water purification                                                             water purification pipes, tubing                                Wood applications                                                                             lazures (wood stains)                                                          wood                                                                           wood products                                                   Miscellaneous  alcohols                                                                       bedding incorporating water or gels                                            ceramic                                                                        contact lens cases-leaching                                                    electronic circuitry                                                           electronics chemicals                                                          enzymes-food production                                                        enzymes                                                                        enzymes-industrial                                                             gel cushions                                                                   marine antifoulants                                                            mildewcides                                                                    wood                                                                           plastics                                                                       laundry                                                                        mining                                                                         natural ruber latex                                                            oil field injection waters including                                           enhanced recover injection fluids,                                             drilling, fracturing and completion                                            fluids                                                                         pipes                                                                          plastics                                                                       polymer systems                                                                polymers and resins (synthetic and                                             natural)                                                                       reagent preservation                                                           rubber                                                                         rubber products                                                                skin remover                                                                   solid protective/decorative films                                              stains                                                                         swimming pools                                                                 waste treatment                                                                water beds                                                      ______________________________________                                    

Because isothiazolones are so active as microbicides and only low levels of halogen-containing organic compounds are required to achieve stabilization, the amount of halogen-containing organic compound in systems being treated will be very small, and therefore it is not likely to interfere with other components in systems requiring protection or with systems to which the protected systems will be applied. Potential areas of general application include metal-working fluids, cooling water, and air washers.

One significant area of application for the compositions of the invention is as microbicides in metal working fluids. Metal working fluids are proprietary combinations of chemicals, which may contain, inter alia, ingredients such as alkanolamines, petroleum sulfonate surfactants, oils (naphthenic, paraffinic, etc.), chlorinated paraffins and fatty esters, sulfurized fatty compounds, phosphate esters, fatty acids and their amine salts, glycols, polyglycols, boric acid esters and amides. They are utilized in the milling, machining, drilling, and other processing technologies for fabricating metal for the purposes of lubricating, cooling, preventing surface corrosion, and the like. They are sold in the form of active metal working fluids (MWF) concentrate, and are diluted in use to 1-10% active ingredients in water.

Because metal working fluids are recycled and stored, the growth of microorganisms is favored. Isothiazolones have been found effective in preventing the growth of such organisms. Certain of the components in the metal working fluids will tend to destroy the isothiazolone and so remove its microbicidal protective activity, so that stabilizers for the isothiazolone against such degradation are desirable.

It is known in the art that the performance of microbicides may be enhanced by combination with one or more other microbicides. Thus, other known microbicides may be combined advantageously with the composition of this invention.

The following examples are intended to illustrate the present invention and not to limit it except as it is limited by the claims. All percentages are by weight unless otherwise specified, and all reagents are of good commercial quality unless otherwise specified. Methods for quantitative determination of the isothiazolones in the following examples in metal-working fluids are described in detail in "Kathon® 886 MW Microbicide and Kathon® 893 MW Fungicide: Analysis in Metalworking Fluids by High-Performance Liquid Chromatography", 1988, Rohm and Haas Company.

EXAMPLE 1

These examples demonstrate the stabilizing effect of halogen-containing organic compounds for isothiazolones added to metal working fluids (MWF). MWF concentrate A was a "semi-synthetic" type having about 10 to 15 percent napthenic/paraffinic oil, about 50 percent water, emulsifying agents, pH adjusting amines, anticorrosive agents, and EP (extreme pressure) agents.

Into a glass vial in the following order were placed: a) 5 parts by weight of the MWF concentrate solution, b) 5 parts of the stabilizer in solution or dispersion, c) 5 parts water, d) 5 parts of an aqueous solution containing 80 ppm active ingredient (AI), prepared by dilution of a 14.4% aqueous solution of an approximately 75/25 mixture of 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone, the former being considered the active ingredient for these purposes; also present was 9.2 weight percent magnesium chloride and 15.7% magnesium nitrate. Thus the final mixture contained 3-5% of the MWF concentrate, 20 ppm active ingredient of the isothiazolone, and 0 (control) to 1,000 ppm of the stabilizer.

The vials were then capped, stored at ambient room temperature in a closed cabinet for a designated time, filtered through a 0.45 micron filter into another vial and analyzed the same day. The relative concentration of the active ingredient was determined by reverse phase high pressure liquid chromatography, utilizing a Varian model 5500 chromatograph and an ultraviolet detector. Tables 1, 2 and 3 summarize the results for a variety of stabilizers representing different aging conditions.

                  TABLE 1                                                          ______________________________________                                         STABILIZATION OF 5-CHLORO-2-METHYL-3-ISOTHIA-                                  ZOLONE IN MWF CONCENTRATE A (aged five days)                                   Original system contained 15-18 ppm 5-chloro-2-methyl-3-                       isothiazolone (Al) with 3% MWF Concentrate A in water.                         All stabilizers were added at 1000 ppm of solution.                                            % Al remaining                                                 Stabilizer        Test #1  Test #2  Test #3                                    ______________________________________                                         None (Control)    20       11       <1                                         N-Bromosuccinimide                                                                               53       56       --                                         N-Iodosuccinimide 42       --       --                                         1,3-Dibromo-5,5-dimethyl-                                                                        54       --       --                                         hydantoin                                                                      3-Bromo-1-chloro-5,5-dimethyl-                                                                   --       65       --                                         hydantoin                                                                      α-Chlorocinnamaldehyde                                                                     --       --       28                                         Dimethylsulfamoyl chloride                                                                       --       --       50                                         ______________________________________                                    

                  TABLE 2                                                          ______________________________________                                         MWF A STABILIZED WITH HALOGEN-CONTAINING                                       ORGANIC COMPOUNDS (aged 4 days)                                                Original system contained 15 ppm 5-chloro-2-methyl-3-iso-                      thiazolone (Al) with 3% MWF concentrate A in water. All                        stabilizers were added at 1000 ppm.                                                            % Al remaining                                                 Stabilizer        Test #1  Test #2  Test #3                                    ______________________________________                                         None (Control)    36       22       38                                         2,2-Dibromo-3-nitrilo-                                                                           73       --       --                                         propionamide                                                                   Bromo-β-nitrostyrene                                                                        54       --       --                                         Bis-(trichloromethyl)sulfone                                                                     67       --       --                                         2-Bromo-2-nitropropanediol                                                                       84       --       --                                         1,2-Dibromo-2,4-dicyanobutane                                                                    70       --       --                                         5,-Bromo-5-nitro-1,3-dioxane                                                                     77       --       --                                         p-Tolyldiiodomethyl sulfone                                                                      56       --       --                                         Morpholine I.sub.2                                                                               --       35       --                                         N-Bromosuccinimde --       31       --                                         N-Iodosuccinimide --       24       --                                         β-Bromostyrene                                                                              --       --       66                                         5-Chlorobenzotriazole                                                                            --       --       100                                        Ethyl dichlorophosphate                                                                          --       --       100                                        ______________________________________                                    

                  TABLE 3                                                          ______________________________________                                         MWF A STABILIZED WITH HALOGEN-CONTAINING                                       ORGANIC COMPOUNDS (aged 3 days)                                                             % Al remaining                                                    Stabilizer     Test # 1  Test #2   Test #3                                     ______________________________________                                         None (Control) 31        26        23                                          Chloroacetic acid                                                                             67        --        --                                          Bromoacetic acid                                                                              52        --        --                                          Iodoacetic acid                                                                               34        --        --                                          Trichloroacetic acid                                                                          57        --        --                                          p-Toluenesulfonyl chloride                                                                    --        37        --                                          Chloramine T   --        --        66                                          Bromomaleic anhydride                                                                         --        --        74                                          Trichloroisocyanuric acid                                                                     --        --        65                                          Povidone I.sub.2                                                                              --        --        30                                          ______________________________________                                    

EXAMPLE 2

This example illustrates the ability of halogen-containing organic compounds to stabilize isothiazolones in the presence of typical formulations used for water treatment in cooling towers.

A synthetic cooling tower water was prepared by adding 466.4 mg sodium carbonate into a liter of deionized water. The pH was adjusted to 9.0 using concentrated hydrochloric acid. Into the solution was added 10.7 ml scale/corrosion inhibitor stock solution (Acrysol® QR 1086, Bahibit™ AM, and Cobratec® TT-50-S), then 160 mg CaCl₂.2H₂ O and 122 mg MgCl₂.6H₂ O. The final solution was adjusted to pH 9.0 with hydrochloric acid.

The synthetic water contained 170 ppm hardness as CaCO₃, 440 ppm alkalinity as CaCO₃, 5 ppm Acrysol® QR 1086, 5 ppm Bahibit™ AM (Phosphonate), and 2 ppm Cobratec® TT-50-S (Tolyltriazole). The hardness was 160 ppm CaCl₂.2H₂ O and 122 ppm MgCl₂.6H₂ O.

Isothiazolone was added at 5 ppm Al and incubated for 10 days at room temperature. Al analysis was done as described in Example 1. Results are given in Table 4.

                  TABLE 4                                                          ______________________________________                                         COMPARISON OF HALOGEN-CONTAINING ORGANIC                                       STABILIZER IN COOLING TOWER WATER AFTER                                        10 DAYS AT ROOM TEMPERATURE                                                                   Stabilizer Level                                                Stabilizer     (ppm)        % Al Remaining                                     ______________________________________                                         None (control)  0           40                                                 1,3-Dichloro-5,5-dimethyl                                                                     50           69                                                 hydantoin                                                                      1,3-Dichloro-5,5-dimethyl                                                                     25           54                                                 hydantoin                                                                      ______________________________________                                    

EXAMPLE 3

This example illustrates the ability of halogen-containing organic compounds to be used in stabiliation of isothiazolones used as mildewcides in paint formulations. The water-based paint formulation was prepared from standard ingredients, utilizing a commercial acrylic-based latex with conventional pigments, dispersants, and the like. The composition is described in Table 5.

To two sealable containers were charged with 100 parts of the paint formulation. To one was charged twice the desired final stabilizer concentration, and to the other, twice the desired isothiazolone concentration. Both portions were homogenized for 15 minutes each, then blended and re-mixed. The sealed containers were stored at 60° C. Samples were removed at 0, 5 and 10 days.

To 1 part of the sample was added 9 parts propylene glycol, the diluted sample shaken for one hour, centrifuged at 70,000 rpm for 30 minutes, the supernatant diluted with two volumes of methanol, and that solution filtered through a 0.45 micron filter. The filtered sample was injected directly into the HPLC described in Example 1. Appropriate analytical calibrations were made for the various isothiazolones studied.

The 4,5-dichloro-2-octyl-3-isothiazolone was added as a 34% solution in xylene. No other salt was present with the 4,5-dichloro-2-octyl-3-isothiazolone when added to form the test mixture. The following formulation is a typical paint blend for testing of stabilization against microbial activity. Texanol® is trimethyl-1,3-pentanediol monisobutyrate supplied by Eastman Chemical. "Latex" is a latex of a copolymer of butyl acrylate and methyl methacrylate.

                  TABLE 5                                                          ______________________________________                                         LATEX PAINT FORMULATION                                                        Material               lb/50 gal                                                                               g/l                                            ______________________________________                                         Natrosol 250 MHR hydroxyethyl cellulose                                                               1.5      3.6                                            Ethylene glycol        12.5     30                                             Premix                                                                         Water                  56.0     134.4                                          Tamol 960 (40%) poly(methacrylic acid)                                                                3.6      8.6                                            Potassium tripolyphosphate                                                                            0.75     1.8                                            Triton CF-10 surfactant                                                                               1.3      3.1                                            Colloid 643 thickener  0.5      1.2                                            Propylene glycol       17.0     40.8                                           Ti-Pure R-902 titanium dioxide                                                                        112.5    270                                            Minex 4 filler pigment 79.7     191.3                                          Icecap K filler pigment                                                                               25.0     60                                             Attagel 50 clay        2.5      6                                              Let Down                                                                       Latex                  153.0    367.1                                          Colloid 643            1.5      3.6                                            Texanol coalescent     4.7      11.3                                           Ammonia (28%           1.16     2.8                                            Natrosol 250 MHR (2.5%)                                                                               53.50    128.4                                          Water                  54.46    130.8                                                                 581.17   1394.9                                         ______________________________________                                    

In Table 6 are presented results for 10 days aging at 60° C.

                  TABLE 6                                                          ______________________________________                                         LATEX PAINT CONTAINING                                                         4,5-DICHLORO-2-OCTYL-3-ISOTHIAZOLONE                                           PRESERVATIVE PLUS HALOGEN-CONTAINING                                           ORGANIC STABILIZERS                                                                               % Al Remaining                                                           Stabilizer  10 days/  15 days/                                    Stabilizers  Level (ppm) 60° C.                                                                            60° C.                               ______________________________________                                         None (control)                                                                                0          0         0                                          N-Bromo-succinimide                                                                         5000        94        52                                          1,3-Dichloro-5,5-                                                                           5000        94        79                                          dimethylhydantoin                                                              ______________________________________                                    

While the invention has been described with reference to specific examples and applications, other modifications and uses for the invention will be apparent to those skilled in the art without departing from the spirit and scope of the invention defined in the appended claims. 

We claim:
 1. A method of stabilizing 3-isothiazolone compounds against chemical degradation in antagonistic environments comprising combining the isothiazolone with an activated halogen-containing organic compound wherein said activated halogen-containing organic compound is selected from the group consisting of N-halosuccinimides, p-toluenesulfonyl halides, alkyl sulfoamoyl halides, haloacetic acids, a-chlorocinnoamaldehyde, p-toluenesulfonyl chloramine sodium salt (chloramine T), bromomaleic anhydride, polyvinylpyrrolidone I₂ complex, morpholine I₂ complex, 5-chlorobenzotriazole, alkyl halohydantoins, halo-substituted triazinetriones, and ethyl dichlorophosphate.
 2. The method according to claim 1 wherein said activated halogen-containing organic compound is combined in a weight ratio to 3-isothiazolone of about 1:10 to 100:1.
 3. The method according to claim 1 wherein said ratio is about 1:1 to 20:1.
 4. The method according to claim 1 wherein said environment is selected from the group consisting of metal working fluid, latex paint, bulk latex, cosmetics, and surfactants.
 5. The method according to claim 1 wherein said 3-isothiazolone is of the formula (I) ##STR3## wherein Y is an unsubstituted or substituted (C₁ -C₈)alkyl, an unsubstituted or substituted (C₃ -C₁₂)cycloalkyl, an unsubstituted or halogen-substituted (C₂ -C₈)alkenyl or alkynyl, an unsubstituted or substituted (C₇ -C₁₀)aralkyl, or an unsubstituted or substituted aryl; and R and R¹ is each independently H, halogen or (C₁ -C₄)alkyl.
 6. The method according to claim 5 wherein Y is selected from: (C₁ -C₈)alkyl or (C₃ -C₁₂)cycloalkyl each optionally substituted with one or more of hydroxy, halo, cyano, alkylamino, dialkylamino, arylamino, carboxy, carbalkoxy, alkoxy, aryloxy, alkylthio, arylthio, haloalkoxy, cycloalkylamino, carbamoxy, or isothiazolonyl; an unsubstituted or halo-substituted (C₂ -C₈)alkenyl or alkynyl; a (C₇ -C₁₀)aralkyl optionally substituted with one or more of halogen, (C₁ -C₄)alkyl or (C₁ -C₄)alkoxy; and an optionally substituted with one or more of halogen, nitro, (C₁ -C₄)alkyl-acylamino, carb(C₁ -C₄)alkoxy or sulfamyl.
 7. The method according to claim 1 wherein said activated halogen-containing organic compound is selected from the group consisting of dichlorodimethylhydantoin, bromochlorodimethylhydantoin, N-bromosuccinimide, N-bromosuccinimide, N-iodosuccinimide, dimethyl sulfamoyl chloride, chloroacetic acid, bromoacetic acid, iodoacetic acid, trichloroacetic acid and p-toluenesulfonyl chloride. 